CN109679327B - Nano organic silicon composite polyurethane waterproof emulsion - Google Patents
Nano organic silicon composite polyurethane waterproof emulsion Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
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- D06M2101/16—Synthetic fibres, other than mineral fibres
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- D06M2101/32—Polyesters
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- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
Abstract
The invention discloses a nano organic silicon composite polyurethane waterproof emulsion which is characterized by comprising the following components in parts by weight: the polyurethane emulsion is compounded by 34-47% of nano-organosilicon emulsion and 53-66% of aqueous polyurethane emulsion by mass percent; the nano organic silicon emulsion is prepared from vinyl nano SiO2The sol, the double-end alkenyl organosilicon monomer, the monovinyl organosilicon monomer, the emulsifier, the water and the initiator are prepared by emulsion polymerization; the waterborne polyurethane emulsion is prepared by the reaction of polyether diol, diisocyanate, dimethylolpropionic acid, a dihydroxysilane monomer, triethylamine, ethylenediamine, a catalyst, an organic solvent and water. The hydrophobicity of the textile surface can be increased by increasing the roughness or modifying the surface with low surface energy materials. Polysiloxane is used as a low surface energy material, the nano silicon dioxide has structural roughness, and the water-based polyurethane is combined, so that the water repellency is good, and the adhesive force of organic silicon is improved.
Description
Technical Field
The invention relates to a waterproof emulsion, which is formed by compounding nano organic silicon emulsion and polyurethane emulsion and belongs to the field of nano functional materials.
Background
Polyurethane is a block polymer, generally consists of flexible long chains of oligomer dihydric alcohol to form chain segments, and consists of polyisocyanate and chain extender to form hard segments, has the advantages of wear resistance, good flexibility, strong adhesive force and the like, and is widely applied in the field of textiles. Waterborne polyurethanes are gradually replacing solvent-borne polyurethanes for environmental reasons. The macromolecular chain of the waterborne polyurethane contains a large number of water-soluble groups, and the waterborne polyurethane is slightly insufficient in the aspects of water resistance, mechanical property and the like.
The invention adopts nano organic silicon emulsion to modify waterborne polyurethane, introduces Si-O-Si and Si-C into an emulsion system, reduces surface energy, improves thermal stability, and improves weather resistance, water resistance and mechanical property of polyurethane.
Disclosure of Invention
The invention aims to provide a nano organic silicon composite polyurethane waterproof emulsion, which is prepared by blending and compounding a nano organic silicon emulsion and a water-based polyurethane emulsion so as to improve the related performance of water-based polyurethane.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows.
A nanometer organosilicon compound polyurethane waterproof emulsion is compounded by nanometer organosilicon emulsion and aqueous polyurethane emulsion, by mass percent, 34-47% of nanometer organosilicon emulsion and 53-66% of aqueous polyurethane emulsion;
the nano organic silicon emulsion is prepared from vinyl nano SiO2The sol, the double-end alkenyl organosilicon monomer (shown as a formula 1), the monovinyl organosilicon monomer (shown as a formula 2), the emulsifier, the water and the initiator are prepared by emulsion polymerization;
(H3C)3Si-O-CH2CH2NH-CH2CH＝CH2formula 2
The waterborne polyurethane emulsion is prepared by the reaction of polyether diol, diisocyanate, dimethylolpropionic acid, a dihydroxysilane monomer (shown in a formula 3), triethylamine, ethylenediamine, a catalyst, an organic solvent and water;
the vinyl nano SiO2Sol catalyzed by vinyl silane coupling agentThe agent, water and emulsifier are prepared by the following steps: adding 6 parts of silane coupling agent KH-570, 1.4 parts of sodium dodecyl sulfate, 1.8 parts of AEO-7 and 0.8 part of PEG-400 into 100 parts of water, stirring and dispersing, adding 2.5 parts of ammonia water under stirring, and continuously stirring and reacting for 4 hours to form vinyl nano SiO2And (3) sol.
The preparation method of the nano organic silicon emulsion comprises the following steps:
(1) adding 250 parts of water and 18 parts of vinyl nano SiO into an emulsifier2Continuously stirring and emulsifying sol, 24 parts of double-end alkenyl organosilicon monomer, 21 parts of monovinyl organosilicon monomer, 2 parts of AEO-9, 2 parts of AEO-7 and 4 parts of sodium dodecyl benzene sulfonate for 0.5h to obtain pre-emulsion;
(2) putting half of the pre-emulsion in a reactor with a temperature control, stirring and condensing device, adding a solution of 0.2 part of initiator and 4 parts of water at 80 ℃, and reacting for 0.5h under heat preservation;
(3) placing the other half of the pre-emulsion in a constant-pressure dropping funnel, slowly dropping the pre-emulsion into a reaction system, simultaneously dropping a solution of 0.4 part of initiator and 10 parts of water, dropping the solution for about 2 hours, controlling the temperature to be 80 ℃, and reacting for 2 hours to obtain nano-organosilicon emulsion;
the preparation method of the waterborne polyurethane emulsion comprises the following steps:
a. adding 180 parts of polyether glycol (N220) into a reactor with a stirrer, a condenser, N2 protection and a thermometer, adding 52 parts of IPDI (isophorone diisocyanate) at 60 ℃ under stirring, and heating to 70 ℃ for reaction for 1.5 hours;
b. adding 9.4 parts of DMPA dissolved in DMF and 0.28 part of dibutyltin dilaurate, and stirring for reaction at 75 ℃ for 0.5 h;
c. cooling to 55 ℃, slowly adding 7 parts of dihydroxy silane monomer (shown as formula 3), reacting until NCO reaches a theoretical value, adding 6 parts of TEA under intensive stirring, and continuously stirring for 0.5 h;
d. cooling to 25 ℃, adding 384 parts of deionized water, quickly stirring for 15min, adding 2.4 parts of ethylenediamine, and reacting for 1.5 h;
e. and removing the acetone in vacuum to obtain the waterborne polyurethane emulsion.
The initiator is one of sodium persulfate, potassium persulfate and ammonium persulfate.
The organic silicon is widely used in textiles, the fabric is endowed with soft and smooth handfeel, the surface energy of the organic silicon is low, and the fabric treated by the organic silicon can obtain good hydrophobicity. However, the adhesion of the silicone on the fabric surface is weak and the washing fastness is poor.
The polyurethane has strong adhesive force and good toughness, and can realize the complementation of the performances of the two materials of the organic silicon polyurethane by blending.
The molecular chain of the polyurethane contains strong polar carbamate and carbamido, so that the polyurethane has strong adhesive force to the fabric, and the compounding of the organic silicon and the polyurethane endows the fabric with good water repellency and simultaneously improves the good adhesive property with the fabric when the composite emulsion is formed into a film. When the emulsion is used for treating the fabric, in the process of forming a film on the surface of the fabric, the organosilicon chain segment with low surface energy migrates to the surface, so that better water repellency is provided; the polyurethane chain segment forms hydrogen bonds and chemical bonds with the fabric through the polar group of the polyurethane chain segment to generate strong adhesion, so that excellent water repellency and adhesion performance are achieved.
The hydrophobicity of the textile surface can be increased by increasing the roughness of its surface or modifying it with a low surface energy substance. The invention takes polysiloxane as a low surface energy material, namely nano silicon dioxide (SiO)2) The structural roughness, combined with the water-based polyurethane, not only realizes good water repellency, but also improves the adhesive force of the organic silicon.
Most of the silicon-containing monomers participating in emulsion polymerization and used for improving emulsion performance are vinyl siloxane coupling agents, and due to the hydrolyzable groups Si-O-C, the groups can be hydrolyzed and condensed to a certain extent in the emulsion polymerization process, so that excessive crosslinking among polymer molecules can be caused to cause instability of polymerization reaction. Although a delayed dropwise addition, addition of a hydrolysis inhibitor is employed in the polymerization process, it is difficult to obtain an effective modification effect. The invention adopts Si (CH)3)3The organosilicon modified monomer of the group has large steric hindrance and is not hydrolyzed, so that the stability of emulsion polymerization is greatly improved, the silicon content in the polymer is increased, the distribution of organosilicon in a polymer molecular chain is more balanced, and the repellency of the polymer is effectively enhancedWater performance.
Detailed Description
The unit "part(s)" of the substance in the present invention means "part(s) by mass".
The preparation methods of the double-terminal alkenyl organosilicon monomer, the single-vinyl organosilicon monomer and the dihydroxy organosilicon monomer are as follows.
The preparation method of the double-terminal alkenyl organosilicon monomer comprises the following steps:
adding a certain amount of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane and octamethylcyclotetrasiloxane into a dry four-neck flask provided with a thermometer and a stirrer, heating to the reaction temperature while stirring, adding a certain amount of trifluoromethanesulfonic acid, and keeping the temperature for reaction for a certain time. After the reaction is finished, anhydrous Na is added2CO3Stirring and neutralizing until pH is 6-7, filtering, and distilling under reduced pressure (90 deg.C, vacuum degree below-0.1 Mpa) to remove unreacted monomer to obtain colorless transparent liquid product. The involved reaction process is shown as (1).
The monovinyl organosilicon monomer is prepared by the reaction of 2- (trimethylsiloxy) ethanolamine and allyl chloride, and the preparation method comprises the following steps:
in a 250mL three-necked flask, 1mol of 2- (trimethylsiloxy) ethanolamine, 1.5mol of triethylamine and 100mL of methylene chloride were added in this order. Placing the three-necked bottle in an ice-water bath, slowly dropwise adding 1.2mol of allyl chloride at the temperature, heating the reaction system to room temperature after dropwise adding, continuously reacting for 1.5 hours at the temperature, stopping the reaction, filtering to remove triethylamine chlorate, distilling under reduced pressure to remove dichloromethane and excessive triethylamine, and collecting fractions to obtain the vinyl organosilicon monomer, namely N-2 (trimethylsiloxy) ethyl enamine. The involved reaction process is shown as (2).
The preparation method of the 2- (trimethylsiloxy) ethanolamine comprises the following steps: adding ethanolamine into a reactor with a mechanical stirrer and a thermometer, stirring and dropwise adding hexamethyldisilazane, reacting at 5-50 ℃ for 0.5-2 h, and obtaining 2- (trimethylsiloxy) ethanolamine through decompression and filtration after the reaction is finished. The molar ratio of ethanolamine to hexamethyldisilazane was 2: 1.
The dihydroxy organic silicon monomer is prepared by reacting diethanolamine, NaOH and trimethylchlorosilane, and the preparation method comprises the following steps:
adding diethanolamine and 0.4mol/L NaOH aqueous solution into a three-neck flask with a stirrer and a reflux condenser, slowly adding trimethylchlorosilane into the flask, reacting at 70 ℃ for 80min after the addition is finished, carrying out reduced pressure distillation, removing redundant water and unreacted diethanolamine, and obtaining N-diethanol-trimethyl silicon (dihydroxy organosilicon monomer); wherein, the molar ratio of the added diethanol amine to the added trimethyl chlorosilane is 1.1:1, and the molar ratio of the trimethyl chlorosilane to the NaOH is 1: 1. The reaction process is shown in (3).
Example 1
A nanometer organosilicon composite polyurethane waterproof emulsion is compounded by nanometer organosilicon emulsion and aqueous polyurethane emulsion, by mass percent, 34% of nanometer organosilicon emulsion and 66% of aqueous polyurethane emulsion;
the nano organic silicon emulsion is prepared from vinyl nano SiO2The sol, the double-end alkenyl organosilicon monomer (shown as a formula 1), the monovinyl organosilicon monomer (shown as a formula 2), the emulsifier, the water and the initiator are prepared by emulsion polymerization;
(H3C)3Si—O-CH2CH2NH-CH2CH＝CH2formula 2
The waterborne polyurethane emulsion is prepared by the reaction of polyether diol, diisocyanate, dimethylolpropionic acid, a dihydroxysilane monomer (shown in a formula 3), triethylamine, ethylenediamine, a catalyst, an organic solvent and water;
the vinyl nano SiO2The sol is prepared from a vinyl silane coupling agent, a catalyst, water and an emulsifier, and the method comprises the following steps: adding 6 parts of silane coupling agent KH-570, 1.4 parts of sodium dodecyl sulfate, 1.8 parts of AEO-7 and 0.8 part of PEG-400 into 100 parts of water, stirring and dispersing, adding 2.5 parts of ammonia water under stirring, and continuously stirring and reacting for 4 hours to form vinyl nano SiO2And (3) sol.
The preparation method of the nano organic silicon emulsion comprises the following steps:
(1) adding 250 parts of water and 18 parts of vinyl nano SiO into an emulsifier2Continuously stirring and emulsifying sol, 24 parts of double-end alkenyl organosilicon monomer, 21 parts of monovinyl organosilicon monomer, 2 parts of AEO-9, 2 parts of AEO-7 and 4 parts of sodium dodecyl benzene sulfonate for 0.5h to obtain pre-emulsion;
(2) putting half of the pre-emulsion in a reactor with a temperature control, stirring and condensing device, adding a solution of 0.2 part of initiator and 4 parts of water at 80 ℃, and reacting for 0.5h under heat preservation;
(3) placing the other half of the pre-emulsion in a constant-pressure dropping funnel, slowly dropping the pre-emulsion into a reaction system, simultaneously dropping a solution of 0.4 part of initiator and 10 parts of water, dropping the solution for about 2 hours, controlling the temperature to be 80 ℃, and reacting for 2 hours to obtain nano-organosilicon emulsion;
the preparation method of the waterborne polyurethane emulsion comprises the following steps:
a. adding 180 parts of polyether glycol (N220) into a reactor with a stirrer, a condenser, N2 protection and a thermometer, adding 52 parts of IPDI (isophorone diisocyanate) at 60 ℃ under stirring, and heating to 70 ℃ for reaction for 1.5 hours;
b. adding 9.4 parts of DMPA dissolved in DMF and 0.28 part of dibutyltin dilaurate, and stirring for reaction at 75 ℃ for 0.5 h;
c. cooling to 55 ℃, slowly adding 7 parts of dihydroxy silane monomer (shown as formula 3), reacting until NCO reaches a theoretical value, adding 6 parts of TEA under intensive stirring, and continuously stirring for 0.5 h;
d. cooling to 25 ℃, adding 384 parts of deionized water, quickly stirring for 15min, adding 2.4 parts of ethylenediamine, and reacting for 1.5 h;
e. and removing the acetone in vacuum to obtain the waterborne polyurethane emulsion.
The initiator is sodium persulfate.
Example 2
A nanometer organosilicon composite polyurethane waterproof emulsion is compounded by nanometer organosilicon emulsion and aqueous polyurethane emulsion, and the nanometer organosilicon emulsion accounts for 41 percent and the aqueous polyurethane emulsion accounts for 59 percent by mass;
the nano organic silicon emulsion is prepared from vinyl nano SiO2The sol, the double-end alkenyl organosilicon monomer (shown as a formula 1), the monovinyl organosilicon monomer (shown as a formula 2), the emulsifier, the water and the initiator are prepared by emulsion polymerization;
(H3C)3Si-O-CH2CH2NH-CH2CH＝CH2formula 2
The waterborne polyurethane emulsion is prepared by the reaction of polyether diol, diisocyanate, dimethylolpropionic acid, a dihydroxysilane monomer (shown in a formula 3), triethylamine, ethylenediamine, a catalyst, an organic solvent and water;
the vinyl nano SiO2The sol is prepared from a vinyl silane coupling agent, a catalyst, water and an emulsifier, and the method comprises the following steps: adding 6 parts of silane coupling agent KH-570, 1.4 parts of sodium dodecyl sulfate, 1.8 parts of AEO-7 and 0.8 part of PEG-400 into 100 parts of waterStirring, dispersing, adding 2.5 parts of ammonia water under stirring, and continuously stirring for reacting for 4 hours to form vinyl nano SiO2And (3) sol.
The preparation method of the nano organic silicon emulsion comprises the following steps:
(1) adding 250 parts of water and 18 parts of vinyl nano SiO into an emulsifier2Continuously stirring and emulsifying sol, 24 parts of double-end alkenyl organosilicon monomer, 21 parts of monovinyl organosilicon monomer, 2 parts of AEO-9, 2 parts of AEO-7 and 4 parts of sodium dodecyl benzene sulfonate for 0.5h to obtain pre-emulsion;
(2) putting half of the pre-emulsion in a reactor with a temperature control, stirring and condensing device, adding a solution of 0.2 part of initiator and 4 parts of water at 80 ℃, and reacting for 0.5h under heat preservation;
(3) placing the other half of the pre-emulsion in a constant-pressure dropping funnel, slowly dropping the pre-emulsion into a reaction system, simultaneously dropping a solution of 0.4 part of initiator and 10 parts of water, dropping the solution for about 2 hours, controlling the temperature to be 80 ℃, and reacting for 2 hours to obtain nano-organosilicon emulsion;
the preparation method of the waterborne polyurethane emulsion comprises the following steps:
a. adding 180 parts of polyether glycol (N220) into a reactor with a stirrer, a condenser, N2 protection and a thermometer, adding 52 parts of IPDI (isophorone diisocyanate) at 60 ℃ under stirring, and heating to 70 ℃ for reaction for 1.5 hours;
b. adding 9.4 parts of DMPA dissolved in DMF and 0.28 part of dibutyltin dilaurate, and stirring for reaction at 75 ℃ for 0.5 h;
c. cooling to 55 ℃, slowly adding 7 parts of dihydroxy silane monomer (shown as formula 3), reacting until NCO reaches a theoretical value, adding 6 parts of TEA under intensive stirring, and continuously stirring for 0.5 h;
d. cooling to 25 ℃, adding 384 parts of deionized water, quickly stirring for 15min, adding 2.4 parts of ethylenediamine, and reacting for 1.5 h;
e. and removing the acetone in vacuum to obtain the waterborne polyurethane emulsion.
The initiator is potassium persulfate.
Example 3
A nanometer organosilicon composite polyurethane waterproof emulsion is compounded by nanometer organosilicon emulsion and aqueous polyurethane emulsion, and the weight percentage of the nanometer organosilicon emulsion is 47 percent, and the weight percentage of the aqueous polyurethane emulsion is 53 percent;
the nano organic silicon emulsion is prepared from vinyl nano SiO2The sol, the double-end alkenyl organosilicon monomer (shown as a formula 1), the monovinyl organosilicon monomer (shown as a formula 2), the emulsifier, the water and the initiator are prepared by emulsion polymerization;
(H3C)3Si-O-CH2CH2NH-CH2CH＝CH2formula 2
The waterborne polyurethane emulsion is prepared by the reaction of polyether diol, diisocyanate, dimethylolpropionic acid, a dihydroxysilane monomer (shown in a formula 3), triethylamine, ethylenediamine, a catalyst, an organic solvent and water;
the vinyl nano SiO2The sol is prepared from a vinyl silane coupling agent, a catalyst, water and an emulsifier, and the method comprises the following steps: adding 6 parts of silane coupling agent KH-570, 1.4 parts of sodium dodecyl sulfate, 1.8 parts of AEO-7 and 0.8 part of PEG-400 into 100 parts of water, stirring and dispersing, adding 2.5 parts of ammonia water under stirring, and continuously stirring and reacting for 4 hours to form vinyl nano SiO2And (3) sol.
The preparation method of the nano organic silicon emulsion comprises the following steps:
(1) adding 250 parts of water and 18 parts of vinyl nano SiO into an emulsifier2Continuously stirring and emulsifying sol, 24 parts of double-end alkenyl organosilicon monomer, 21 parts of monovinyl organosilicon monomer, 2 parts of AEO-9, 2 parts of AEO-7 and 4 parts of sodium dodecyl benzene sulfonate for 0.5h to obtain pre-emulsion;
(2) putting half of the pre-emulsion in a reactor with a temperature control, stirring and condensing device, adding a solution of 0.2 part of initiator and 4 parts of water at 80 ℃, and reacting for 0.5h under heat preservation;
(3) placing the other half of the pre-emulsion in a constant-pressure dropping funnel, slowly dropping the pre-emulsion into a reaction system, simultaneously dropping a solution of 0.4 part of initiator and 10 parts of water, dropping the solution for about 2 hours, controlling the temperature to be 80 ℃, and reacting for 2 hours to obtain nano-organosilicon emulsion;
the preparation method of the waterborne polyurethane emulsion comprises the following steps:
a. adding 180 parts of polyether glycol (N220) into a reactor with a stirrer, a condenser, N2 protection and a thermometer, adding 52 parts of IPDI (isophorone diisocyanate) at 60 ℃ under stirring, and heating to 70 ℃ for reaction for 1.5 hours;
b. adding 9.4 parts of DMPA dissolved in DMF and 0.28 part of dibutyltin dilaurate, and stirring for reaction at 75 ℃ for 0.5 h;
c. cooling to 55 ℃, slowly adding 7 parts of dihydroxy silane monomer (shown as formula 3), reacting until NCO reaches a theoretical value, adding 6 parts of TEA under intensive stirring, and continuously stirring for 0.5 h;
d. cooling to 25 ℃, adding 384 parts of deionized water, quickly stirring for 15min, adding 2.4 parts of ethylenediamine, and reacting for 1.5 h;
e. and removing the acetone in vacuum to obtain the waterborne polyurethane emulsion.
The initiator is ammonium persulfate.
The nano organic silicon composite polyurethane waterproof emulsion of the 3 examples is light blue and semitransparent, and is not layered or precipitated after being centrifuged for 1h at 3000 r/min. (test according to the method of < GB/T11175-2002 synthetic resin emulsion test method)
The nano organic silicon composite polyurethane waterproof emulsion of the 3 embodiments is used for waterproof finishing of polyester fabrics, and the formula is as follows: 20 parts of nano organic silicon composite polyurethane waterproof emulsion, 2 parts of thickening agent and 78 parts of water; the process comprises the following steps: coating → prebaking (90 ℃, 3min) → baking (160 ℃, 90s), wherein the polyester fabric comprises 100% of polyester and 150D-150D in terms of components and specifications. With reference to methods GB/T4745-2012 and GB/T4744-2013, the polyester fabric after coating is subjected to water resistance and water repellency tests, and the results are shown in Table 1.
TABLE 1 Water resistance and Water resistance of polyester coating samples
| Test specimen | Water repellency/grade | Water repellency/grade (after washing) | Water repellency (hydrostatic pressure)/KPa |
| Example 1 | 4 | 3 | 47.3 |
| Example 2 | 5 | 4 | 51.6 |
| Example 3 | 5 | 4 | 54.2 |
After the polyester fabric is finished by the nano organic silicon composite polyurethane waterproof emulsion coating, the water repellency grade is more than 4 grade, the hydrostatic pressure is more than 47KPa, and the waterproof and water-repellent performance is excellent.
Claims (4)
1. A nanometer organic silicon composite polyurethane waterproof emulsion is characterized in that: the polyurethane emulsion is compounded by 34-47% of nano-organosilicon emulsion and 53-66% of aqueous polyurethane emulsion by mass percent;
the nano organic silicon emulsion is prepared from vinyl nano SiO2The sol, the double-end alkenyl organosilicon monomer shown in the formula 1, the monovinyl organosilicon monomer shown in the formula 2, an emulsifier, water and an initiator are prepared by emulsion polymerization;
(H3C)3Si-O-CH2CH2NH-CH2CH＝CH2formula 2
The waterborne polyurethane emulsion is prepared by the reaction of polyether diol, diisocyanate, dimethylolpropionic acid, a dihydroxysilane monomer shown in a formula 3, triethylamine, ethylenediamine, a catalyst, an organic solvent and water;
the vinyl nano SiO2The sol is prepared from a vinyl silane coupling agent, a catalyst, water and an emulsifier, and the method comprises the following steps: adding 6 parts of silane coupling agent KH-570, 1.4 parts of sodium dodecyl sulfate, 1.8 parts of AEO-7 and 0.8 part of PEG-400 into 100 parts of water, stirring and dispersing, adding 2.5 parts of ammonia water under stirring, and continuously stirring and reacting for 4 hours to form vinyl nano SiO2Sol;
the preparation method of the double-terminal alkenyl organosilicon monomer comprises the following steps:
adding a certain amount of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane and octamethylcyclotetrasiloxane into a dry four-neck flask provided with a thermometer and a stirrer, heating to the reaction temperature while stirring, adding a certain amount of trifluoromethanesulfonic acid, keeping the temperature for reaction for a certain time, and adding anhydrous Na after the reaction is finished2CO3Stirring for neutralizing until pH is 6-7, filtering, distilling at 90 deg.C under vacuum degree of-0.1 Mpa, removing unreacted monomer to obtain colorless transparent liquid product, and reactingThe process is shown as (1);
the monovinyl organosilicon monomer is prepared by the reaction of 2- (trimethylsiloxy) ethanolamine and allyl chloride, and the preparation method comprises the following steps:
sequentially adding 1mol of 2- (trimethylsiloxy) ethanolamine, 1.5mol of triethylamine and 100mL of dichloromethane into a 250mL three-necked bottle, placing the three-necked bottle into an ice water bath, slowly dropwise adding 1.2mol of allyl chloride at the temperature, heating a reaction system to room temperature after the dropwise adding is finished, continuing to react for 1.5 hours at the temperature, stopping the reaction, filtering to remove triethylamine chlorate, carrying out reduced pressure distillation to remove dichloromethane and excessive triethylamine, collecting fractions to obtain a vinyl organosilicon monomer, and N-2 (trimethylsiloxy) ethyl enamine, wherein the involved reaction process is shown in (2);
the preparation method of the 2- (trimethylsiloxy) ethanolamine comprises the following steps: adding ethanolamine into a reactor with a mechanical stirrer and a thermometer, stirring and dropwise adding hexamethyldisilazane, reacting at 5-50 ℃ for 0.5-2 h, and after the reaction is finished, performing reduced pressure filtration to obtain 2- (trimethylsiloxy) ethanolamine, wherein the molar ratio of the ethanolamine to the hexamethyldisilazane is 2: 1;
the dihydroxy silane monomer is prepared by reacting diethanol amine, NaOH and trimethylchlorosilane, and the preparation method comprises the following steps:
adding diethanolamine and 0.4mol/L NaOH aqueous solution into a three-neck flask with a stirrer and a reflux condenser, slowly adding trimethylchlorosilane into the flask, reacting at 70 ℃ for 80min after the addition is finished, carrying out reduced pressure distillation, removing redundant water and unreacted diethanolamine, and obtaining N-diethanol-trimethylsilane, namely a dihydroxysilane monomer; wherein, the molar ratio of the added diethanol amine to the added trimethyl chlorosilane is 1.1:1, the molar ratio of the trimethyl chlorosilane to the added NaOH is 1:1, and the reaction process is shown as (3)
2. The nano-organosilicon composite polyurethane waterproof emulsion according to claim 1, characterized in that: the preparation method of the nano organic silicon emulsion comprises the following steps:
(1) adding 250 parts of water and 18 parts of vinyl nano SiO into an emulsifier2Continuously stirring and emulsifying sol, 24 parts of double-end alkenyl organosilicon monomer, 21 parts of monovinyl organosilicon monomer, 2 parts of AEO-9, 2 parts of AEO-7 and 4 parts of sodium dodecyl benzene sulfonate for 0.5h to obtain pre-emulsion;
(2) putting half of the pre-emulsion in a reactor with a temperature control, stirring and condensing device, adding a solution of 0.2 part of initiator and 4 parts of water at 80 ℃, and reacting for 0.5h under heat preservation;
(3) and (3) placing the other half of the pre-emulsion into a constant-pressure dropping funnel, slowly dropping the pre-emulsion into a reaction system, simultaneously dropping a solution of 0.4 part of initiator and 10 parts of water, finishing dropping within 2 hours, controlling the temperature to be 80 ℃, and reacting for 2 hours to obtain the nano organic silicon emulsion.
3. The nano-organosilicon composite polyurethane waterproof emulsion according to claim 1, characterized in that: the preparation method of the waterborne polyurethane emulsion comprises the following steps:
a. adding 180 parts of polyether glycol N220 into a reactor with a stirrer, a condenser and N2Adding 52 parts of IPDI (isophorone diisocyanate) into a reactor with a protection thermometer at 60 ℃ under stirring, and heating to 70 ℃ for reaction for 1.5 h;
b. adding 9.4 parts of DMPA dissolved in DMF and 0.28 part of dibutyltin dilaurate, and stirring for reaction at 75 ℃ for 0.5 h;
c. cooling to 55 ℃, slowly adding 7 parts of dihydroxy silane monomer shown as formula 3, reacting until NCO reaches a theoretical value, adding 6 parts of TEA under intensive stirring, and continuously stirring for 0.5 h;
d. cooling to 25 ℃, adding 384 parts of deionized water, quickly stirring for 15min, adding 2.4 parts of ethylenediamine, and reacting for 1.5 h;
e. and removing the acetone in vacuum to obtain the waterborne polyurethane emulsion.
4. The nano-organosilicon composite polyurethane waterproof emulsion according to any one of claims 1 to 3, characterized in that: the initiator is one of sodium persulfate, potassium persulfate and ammonium persulfate.
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| CN110965349A (en) * | 2019-10-28 | 2020-04-07 | 杭州芮缦博布艺有限公司 | Waterproof soft finishing agent for polyester sofa cloth, preparation method and use method |
| CN110983801A (en) * | 2019-12-24 | 2020-04-10 | 南通赛晖科技发展股份有限公司 | Preparation method of waterproof moisture-permeable cotton fabric |
| CN111234167B (en) * | 2020-04-03 | 2021-02-19 | 赵牧青 | Preparation method of high-stability organic silicon modified waterborne polyurethane |
| CN113603858A (en) * | 2021-08-20 | 2021-11-05 | 上海涂固安高科技有限公司 | Water-based polymer inorganic composite nano-particles and application thereof |
| CN113789672B (en) * | 2021-09-22 | 2023-09-22 | 安徽安利材料科技股份有限公司 | Polyurethane synthetic leather for outdoor sport casual shoes and preparation method thereof |
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